CN103880735B - A kind of smectic liquid crystal compound and preparation method thereof and application - Google Patents
A kind of smectic liquid crystal compound and preparation method thereof and application Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- 239000004990 Smectic liquid crystal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 21
- 230000003287 optical effect Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 6
- 238000004891 communication Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JNFRNXKCODJPMC-UHFFFAOYSA-N aniline;boric acid Chemical compound OB(O)O.NC1=CC=CC=C1 JNFRNXKCODJPMC-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a kind of smectic liquid crystal compound and preparation method thereof and application.This smectic liquid crystal compound, its general structure is such as formula shown in V, and in described formula V, n is the integer of 2-8.Liquid crystalline cpd shown in formula V provided by the invention has wider smectic liquid crystal temperature range, higher optical anisotropy and larger dielectric anisotropy, the host compound in mixed liquid crystal used can be shown as smectic phase multistable, also can have the compound of large optical birefringence rate mixed liquid crystal as preparation, thus need well to be applied in the display of large optical birefringence mixed liquid crystal material and optical communication in the display of smectic phase multistable state liquid srystal and other.
Description
Technical field
The present invention relates to a kind of smectic liquid crystal compound and preparation method thereof and application.
Background technology
1888, Austria botanist F.Reinitzer is when measuring melting points of organic compounds, find that some organic compound experienced by an opaque muddy liquid phase after thawing, continue heating, just become transparent isotropic liquid, the liquid mesophase spherule of this muddiness has the phenomenon similar with crystal, therefore is called liquid crystal (liquidcrystal).Thereafter between decades, through long-term development, to enrich and perfect liquid crystal birefringence is theoretical, liquid crystal phase is theoretical, X-ray diffraction studies liquid crystal structure analyzes (mainly smectic phase), specific conductivity, elastic constant, specific inductivity, order parameter etc.
Because the arrangement situation of liquid crystal molecule, molecular configuration and molecular interaction there are differences, in certain temperature range, liquid crystal molecule has different liquid crystalline phase structure, and the phase structure of liquid crystal has following several usually:
(1) nematic phase (nematicphase): the feature of nematic phase structure can be summarized as follows: nematic phase is molecular by bar-shaped (strip, disk like), molecule barycenter does not have long-range order, there is the mobility being similar to common fluid, molecule does not arrange stratification, can slide by up, down, left, right, before and after, only be parallel to each other in molecular long axis direction (director) upper maintenance or be bordering on parallel, intermolecular shot-range interaction is faint.
(2) smectic phase (smecticphase): the feature of smectic phase structure is: smectic phase is molecular by bar-shaped (strip, disk like), molecule can arrange stratification, in layer, molecular long axis is parallel to each other, and its direction perpendicular to layer plane, also can become oblique arrangement with layer plane.Because molecular arrangement is neat, its regularity is close to crystal, there is sequential 2 D, molecule centroid position is unordered in layer, can free shift, thus has mobility, but viscosity is larger, molecule can slide front, rear, left and right in layer, but can not move between upper and lower, thus has the order of solid height.
(3) chiral liquid crystal (chiralliquidcrystal): the feature of chiral liquid crystal compounds is have one or more unsymmetrical carbon in molecule, due to the existence of unsymmetrical carbon (C*), the structures and characteristics of such liquid crystal and nematic phase and smectic phase is made to have very large difference.Cholesteryl phase (cholestericphase), blue phase (bluephase) and ferroelectric liquid crystals phase (ferroelectricphase) etc. are comprised again at chiral liquid crystal compounds.
At traditional twisted nematic (TN-LCD), in the liquid-crystal display of super-twist nematic (STN-LCD) and film transistor type (TFT-LCD), the liquid crystal material adopted is all the Nematic phase liquid crystal material with certain temperature range, the feature of this kind of display can overturn when liquid crystal molecule is under electric field action, when polarized light is by after liquid crystal device, the OFF state (without electric field action) of liquid crystal molecule and ON state (having electric field action) produce the change of contrast gradient, thus realize display, but after electric field is withdrawn, liquid crystal molecule can return to OFF state again, display effect disappears.
The multistable display of liquid crystal, mainly comprise the display of smectic phase multistable and the display of cholesteryl phase multistable etc. at present, its cardinal principle is that liquid crystal molecule can be adjusted to the state with different optical characteristic under electric field action, and this state with different optical characteristic can also continue to keep after electric field is withdrawn.The feature of this kind of display is shown content when can preserve for a long time without when power consumption, and this kind of display is without backlight, does not also need polaroid, and therefore manufacturing cost is lower.Current this kind of display is more and more applied in multiple fields such as electronic tag, public display board and intelligent dimming glass.
In the display of smectic phase multistable state liquid srystal, more and more higher requirement is proposed to liquid crystal material, comprises wider smectic phase temperature range to keep wide displays temperature scope; Higher optical birefringence rate makes smectic liquid crystal keep higher scattered power when scattering states, thus improves the contrast gradient of display; Larger dielectric anisotropy is in order to reduce the driving voltage etc. of liquid-crystal display.The people such as Newton in 1994 at JournalofMaterialsChemistry(1994,4(6), the smectic liquid crystal reported 869-874) containing siloxanes and biphenyl cyano group group manifests for smectic phase multistable, and driving voltage is lower, but temperature range is narrower and contrast gradient is not high.
Summary of the invention
The object of this invention is to provide a kind of smectic liquid crystal compound and preparation method thereof and application.
Smectic liquid crystal compound provided by the invention, its general structure such as formula shown in V,
In described formula V, n is the integer of 2-8;
Concrete, n is 4;
Shown in the described formula V of preparation provided by the invention, the method for compound, comprises the steps:
Compound shown in formula IX and thiophosgene are reacted, reacts complete and obtain compound shown in described formula V.
In described formula IX, n is the integer of 2-8.
In aforesaid method, the molar ratio of compound shown in formula IX and thiophosgene is 1-1:1-3, is specially 1:1.4;
In described reactions steps, temperature is 0 DEG C-25 DEG C, is specially 0-5 DEG C, and the time is 1-10 hour; Reaction end is determined by a plate, is reaction end when point plate shows without raw material.
Solvent is selected from least one in methylene dichloride, trichloromethane and tetracol phenixin.The consumption of solvent is as the criterion with complete solubilizing reaction thing.
In addition, with compound shown in the liquid-crystal composition of compound effective constituent shown in above-mentioned formula V provided by the invention and formula V preparing the application in liquid-crystal composition, also protection scope of the present invention is belonged to.
Wherein, prepare the method for midbody compound used in compound shown in above-mentioned formula V, comprise the steps:
1) compound shown in compound and formula VIII shown in formula VII is carried out linked reaction 2-10 hour in 50 DEG C-150 DEG C under the effect of catalyzer, sodium carbonate, toluene, second alcohol and water, react complete and obtain compound shown in described formula VI;
2) at triphenylphosphine, Pd(PPh
3)
2cl
2, cuprous iodide, triethylamine and tetrahydrofuran (THF) existence under, be that 1-1:1-2 carries out linked reaction 2-10 hour in 50 DEG C-150 DEG C by compound shown in compound and formula X shown in step 1) gained formula VI with molar ratio, react complete and obtain compound shown in described formula IX;
In described formula X, n is the integer of 2-8.
In the step 1) of aforesaid method, catalyzer is selected from four (triphenylphosphines) and closes at least one in palladium, two (triphenylphosphine) palladium chloride, palladium and palladium/carbon catalyst;
Shown in described formula VII, the molar ratio of compound shown in compound and formula VIII is 1-1:1-2, is specially 1:1.05; The molar ratio of compound, catalyzer, sodium carbonate shown in described formula VII is 1-1:0.01-0.05:2-5, is specially 1:0.01:2.5.
Such liquid crystalline cpd provided by the invention has wider smectic liquid crystal temperature range, higher optical anisotropy and larger dielectric anisotropy, the host compound in mixed liquid crystal used can be shown as smectic phase multistable, also can have the compound of large optical birefringence rate mixed liquid crystal as preparation, thus need well to be applied in the display of large optical birefringence mixed liquid crystal material and optical communication in the display of smectic phase multistable state liquid srystal and other.
Accompanying drawing explanation
Fig. 1 is 5-(oneself-1-alkynes)-2-(4-isothiocyano) the liquid crystal behaviors figure of pyridine.
Fig. 2 is 5-(oneself-1-alkynes)-2-(4-isothiocyano) the infrared figure of pyridine.
Fig. 3 is 5-(oneself-1-alkynes)-2-(4-isothiocyano) pyridine
1hNMR schemes.
Fig. 4 is 5-(oneself-1-alkynes)-2-(4-isothiocyano) the MS figure of pyridine.
Fig. 5 is 5-(oneself-1-alkynes)-2-(4-isothiocyano) the DSC figure of pyridine.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
In following embodiment, shown in ownership formula IX used, the preparation method of the reactant of compound is as follows:
One, 4-(5-bromopyridine-2-base) preparation of aniline
2,5-dibromo pyridine 20g(0.084mol is added in there-necked flask), the hydrochloride 15.4g(0.089mol of 4-amino-benzene boric acid), sodium carbonate 22g, toluene 100ml, ethanol 50ml, water 10ml, adds four (triphenylphosphines) and closes palladium (0) 0.5 gram after nitrogen purge; Be warming up to 105 DEG C, reflux more than 4 hours, monitor by gas-chromatography (GC) in reaction process, when GC display is without stopped reaction after 2,5-dibromo pyridines, cool to room temperature, separatory, aqueous phase ethyl acetate is extracted, and merges organic phase, saturated common salt washing once, after concentrated organic phase, recrystallization after silica gel (200-300 order) post, obtains 16.2g white solid excessively, GC purity >99%, yield 77.5%.
Two, the preparation of 4-(5-(oneself-1-alkynes) pyridine-2-base) aniline
4-(5-bromopyridine-2-base is added in there-necked flask) aniline 10g(0.04mol), triphenylphosphine 1.5g, Pd(PPh3) and 2Cl20.6g, cuprous iodide 0.4g, triethylamine 100ml, tetrahydrofuran (THF) 100ml.After nitrogen purge, add 1-hexin 5g(0.061mol), be warming up to 105 DEG C, reflux more than 3 hours, monitor with GC in reaction process, when GC display is without 4-(5-bromopyridine-2-base) stopped reaction after aniline, by reaction solution cool to room temperature.Carry out separatory after adding ethyl acetate and water, aqueous phase extracts by ethyl acetate again, then merges organic phase, washes once with saturated common salt.After concentrated organic phase, after crossing silica gel (200-300 order) post, recrystallization obtains yellow solid 7.4g, GC purity > 99%, yield 75%.
According to upper identical method, only replace the substituting group of respective reaction thing according to product structure, following each compound can be obtained:
4-(5-(fourth-1-alkynes) pyridine-2-base) aniline,
4-(5-(penta-1-alkynes) pyridine-2-base) aniline,
4-(5-(-1-alkynes in heptan) pyridine-2-base) aniline,
4-(5-(pungent-1-alkynes) pyridine-2-base) aniline,
4-(5-(-1-alkynes in the ninth of the ten Heavenly Stems) pyridine-2-base) aniline,
4-(5-(-1-alkynes in the last of the ten Heavenly stems) pyridine-2-base) aniline.
Embodiment 1,5-(oneself-1-alkynes)-2-(4-isothiocyano) preparation of pyridine
4-(5-(oneself-1-alkynes) pyridine-2-base) aniline 10g(0.04mol is added in there-necked flask), calcium carbonate 12g(0.12mol), methylene dichloride 100ml, water 50ml.Be cooled to 0 degree Celsius, drip thiophosgene 6.5g(0.056mol), keep temperature 0 ~ 5 DEG C to stir more than 1 hour, some plate is determined can process without raw material.By the product suction strainer of reaction, then use 20ml washed with dichloromethane filter cake, obtain yellow organic phase by after filtrate separatory, concentrated organic phase, after crossing silica gel (200-300 order) post, recrystallization obtains 5.0g white solid, GC purity > 99.5%, yield 43%.
Structural identification data are as follows:
IR(is as shown in Figure 2) (KBr) ν max/cm-1:2960,2933,2860,2181,2038,1576,1540,1475,1369,1300,1174,1105,1039,930,827,758,712,650,636,511
1HNMR(is as shown in Figure 3) (300MHz) δ: 8.67-8.68(d, 1H), 7.98-8.00 (d, 2H), 7.73-7.75 (m, 1H), 7.62-7.65 (d, 1H), 7.30-7.32 (2,2H), 2.42-2.46 (t, 2H), 1.59-1.61 (m, 2H), 1.47-1.49 (m, 2H), 0.93-0.95 (t, 3H)
MS (m/z) (as shown in Figure 4): 292 (M+), 277,263,249,236,222,219,204,190,165,159,101
As from the foregoing, this product structure is correct, and for belonging to the compound of formula IX, wherein, n is 4;
In addition, this compound has the texture of smectic phase, and as shown in Figure 1, shown in Fig. 5, its liquid crystal phase temperature range (DSC) is its liquid crystal behaviors figure: C41.1 DEG C of SA129.4 DEG C of I.
This compound, owing to being at room temperature crystal, therefore measures its dielectric anisotropy and refractive anisotrop by extrapotation:
With TEB110(Shijiazhuang Chengzhi Yonghua Display Materials Co., Ltd. product) be parent mixed liquid crystal, this liquid crystalline cpd is by 10%(W/W) be dissolved in TEB110, under 20 DEG C of conditions with 1KHz, the ε of this liquid crystalline cpd is tested by capacitance method || with ε ⊥, and calculate the △ ε of this liquid crystal compound, thus calculate the ε of this liquid crystalline cpd pure || with ε ⊥, and calculate the △ ε of this liquid crystalline cpd, test result is listed in table 1.
Utilize Abbe refractometer, measure ne and no of above-mentioned liquid crystal compound, and calculate the △ ε of this liquid crystal compound.Thus calculate ne and no of this pure liquid crystalline cpd, and calculate the △ n of this liquid crystalline cpd, test result is listed in table 1.
Wherein, the method for calculation of △ ε and △ n are as follows:
Parent liquid crystal TEB110(B) parameter ε || (B), ε ⊥ (B) and △ ε (B) are in table 1, by liquid crystalline cpd (A) by 10%(W/W) be dissolved in parent liquid crystal TEB110, under 20 DEG C of conditions with 1KHz, the ε of this liquid crystal compound is tested by capacitance method || with ε ⊥, and calculate the △ ε of this liquid crystal compound, △ ε=ε ||-ε ⊥.
According to the additivity of liquid crystalline cpd dielectric anisotropy, calculate ε || (A), ε ⊥ (A), △ ε (A)
ε||=ε||(A)×10%+ε||(B)×90%ε||(A)=[ε||-ε||(B)×90%]/10%
ε⊥=ε⊥(A)×10%+ε⊥(B)×90%ε⊥(A)=[ε⊥×10%+ε⊥(B)×90%]/10%
△ε(A)=ε||(A)-ε⊥(A)
Parent liquid crystal TEB110(B) parameter ne (B), no (B) and △ n (B) in table 1, by liquid crystalline cpd (A) by 10%(W/W) be dissolved in parent liquid crystal TEB110, Abbe refractometer is utilized to measure ne, no of liquid crystal compound, and calculate the △ n of this liquid crystal compound, △ n=ne-no.
According to the additivity of liquid crystalline cpd refractive anisotrop, calculate ne (A), no (A) and △ n (A)
ne=ne(A)×10%+ne(B)×10%ne(A)=[ne-ne(B)×10%]/10%
no=no(A)×10%+no(B)×90%no(A)=[no×10%+no(B)×90%]/10%
△n(A)=ne(A)-no(A)
Table 1,5-(oneself-1-alkynes)-2-(4-isothiocyano) measurement result of pyridine liquid crystalline cpd
| ne | no | △n | ε|| | ε⊥ | △ε | |
| TEB110(B) | 1.6400 | 1.5030 | 0.1370 | 14.6 | 6.0 | 8.6 |
| Liquid crystal compound | 1.6643 | 1.5045 | 0.1598 | 15.2 | 6.1 | 9.1 |
| Liquid crystal | 1.8833 | 1.5182 | 0.3651 | 20.9 | 7.3 | 13.6 |
Obtained by extrapotation, the dielectric anisotropy △ ε of this liquid crystal is 13.6, and refractive anisotrop △ n is 0.3651.
According to upper identical method, only replace the substituting group of respective reaction thing according to product structure, following each compound can be obtained:
5-(fourth-1-alkynes)-2-(4-isothiocyano) pyridine,
5-(penta-1-alkynes)-2-(4-isothiocyano) pyridine,
5-(-1-alkynes in heptan)-2-(4-isothiocyano) pyridine,
5-(pungent-1-alkynes)-2-(4-isothiocyano) pyridine,
5-(-1-alkynes in the ninth of the ten Heavenly Stems)-2-(4-isothiocyano) pyridine,
5-(-1-alkynes in the last of the ten Heavenly stems)-2-(4-isothiocyano) pyridine.
Above-mentioned data show, liquid crystalline cpd shown in formula V provided by the invention has wider smectic liquid crystal temperature range, higher optical anisotropy and larger dielectric anisotropy, the host compound in mixed liquid crystal used can be shown as smectic phase multistable, also can have the compound of large optical birefringence rate mixed liquid crystal as preparation, thus need well to be applied in the display of large optical birefringence mixed liquid crystal material and optical communication in the display of smectic phase multistable state liquid srystal and other.
Claims (9)
1. the compound of smectic liquid crystal shown in formula V,
In described formula V, n is the integer of 2-8.
2. prepare a method for the compound of smectic liquid crystal shown in formula V described in claim 1, comprise the steps:
Compound shown in formula IX and thiophosgene are reacted, reacts complete and obtain smectic liquid crystal compound shown in described formula V;
In described formula IX, n is the integer of 2-8.
3. method according to claim 2, is characterized in that: the molar ratio of compound and thiophosgene shown in described formula IX is 1:1-1:3.
4. method according to claim 3, is characterized in that: the molar ratio of compound and thiophosgene shown in described formula IX is 1:1.4.
5. method according to claim 2, is characterized in that: in described reactions steps, and temperature is 0 DEG C-25 DEG C.
6. method according to claim 2, is characterized in that: in described reactions steps, and the time is 1-10 hour.
7., according to the arbitrary described method of claim 2-6, it is characterized in that: described reaction solvent for use is selected from least one in methylene dichloride, trichloromethane and tetracol phenixin.
8. with the liquid-crystal composition that the compound of smectic liquid crystal shown in formula V described in claim 1 is effective constituent.
9. described in claim 1, the compound of smectic liquid crystal shown in formula V is preparing the application in liquid-crystal composition.
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| EP1054001A1 (en) * | 1999-05-19 | 2000-11-22 | MERCK PATENT GmbH | Isothiocyanate tolanes and liquid crystal mixtures containing them |
| CN102433133A (en) * | 2011-09-14 | 2012-05-02 | 深圳超多维光电子有限公司 | Nematic liquid crystal composition |
| CN102786456A (en) * | 2012-07-26 | 2012-11-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing isothiocyanic acid radical as well as preparation method and application thereof |
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| EP1054001A1 (en) * | 1999-05-19 | 2000-11-22 | MERCK PATENT GmbH | Isothiocyanate tolanes and liquid crystal mixtures containing them |
| CN102433133A (en) * | 2011-09-14 | 2012-05-02 | 深圳超多维光电子有限公司 | Nematic liquid crystal composition |
| CN102786456A (en) * | 2012-07-26 | 2012-11-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing isothiocyanic acid radical as well as preparation method and application thereof |
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| Title |
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| 彭增辉等.二苯乙炔基异硫氰酸酯的合成与液晶性质研究.《液晶与显示》.2011,第26卷(第4期),第428页图1、左栏第1-2段. * |
| 彭增辉等.双环NCS液晶的合成与性能研究.《液晶与显示》.2009,第24卷(第5期),第630-634页. * |
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